U.S. patent number 5,241,014 [Application Number 07/639,479] was granted by the patent office on 1993-08-31 for process for the production of largely amorphous polyalphaolefins with a narrow molecular weight distribution.
This patent grant is currently assigned to Huels Aktiengesellschaft. Invention is credited to Helmut Kehr, Adolf Kuhnle, Heinrich Leppek, Matthias Schleinzer.
United States Patent |
5,241,014 |
Kehr , et al. |
August 31, 1993 |
Process for the production of largely amorphous polyalphaolefins
with a narrow molecular weight distribution
Abstract
A process for the production of largely amorphous
polyalphaolefins with a narrow molecular weight distribution is
provided where the products exhibit the following features:
softening point between 70.degree. and 40.degree. C.; melt
viscosity (190.degree. C.) between 1,000 and 100,000 mPas; density
less than 0.90 g/cm.sup.3 ; needle penetration between 5 and 50 0.1
mm; and maximum molecular inhomogeneity 6. These polymers are
obtained by a radical decomposition performed at high temperatures
on copolymers based on C.sub.4-10 alpha-olefins, propene and
optionally ethene. The products are suitable for use as hot melt
adhesives as well as for heavy coating compounds.
Inventors: |
Kehr; Helmut (Schermbeck,
DE), Kuhnle; Adolf (Marl, DE), Leppek;
Heinrich (Gelsenkirchen-Buer, DE), Schleinzer;
Matthias (Dorsten, DE) |
Assignee: |
Huels Aktiengesellschaft (Marl,
DE)
|
Family
ID: |
6397925 |
Appl.
No.: |
07/639,479 |
Filed: |
January 10, 1991 |
Foreign Application Priority Data
|
|
|
|
|
Jan 12, 1990 [DE] |
|
|
4000695 |
|
Current U.S.
Class: |
525/376;
525/333.7; 525/333.8; 525/387 |
Current CPC
Class: |
C08F
8/50 (20130101); B29C 48/92 (20190201); C08F
8/50 (20130101); C08F 210/16 (20130101); B29C
48/395 (20190201); B29C 48/022 (20190201); C08F
2810/10 (20130101); B29C 2948/92704 (20190201) |
Current International
Class: |
C08F
8/00 (20060101); C08F 8/50 (20060101); C08F
008/50 () |
Field of
Search: |
;525/387,376 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
4833209 |
May 1989 |
Beijleveld et al. |
5037895 |
August 1991 |
Marker et al. |
5047485 |
September 1991 |
De Nicola, Jr. |
|
Primary Examiner: Lipman; Bernard
Attorney, Agent or Firm: Millen, White, Zelano &
Branigan
Claims
What is claimed is:
1. A process for the production of substantially amorphous
polyalphaolefins having a softening point between 70.degree. and
140.degree. C., a melt viscosity at 190.degree. C. between 1,000
and 100,000 mPas, a density less than 0.90 g/cm.sup.3, a needle
penetration of 5 to 50 0.1 mm and a molecular inhomogeneity,
determined by gel permeation chromatography, of at most 6,
said process comprising reducing the melt viscosity determined at
190.degree. C., of a substantially amorphous polyalphaolefin
starting material in the presence of a radical donor under shear
stress at a temperature above the softening point of the
polyalphaolefin, wherein the substantially amorphous
polyalphaolefin starting material has the following monomer
composition:
3 to 75% by weight of an alpha-olefin with 4 to 10 carbon
atoms,
25 to 95% by weight of propene and
0 to 20% by weight of ethene, and
a softening point between 70.degree. and 140.degree. C., a melt
viscosity at 190.degree. C. between 5,000 and 200,000 mPas, a
density less than 0.90 g/cm.sup.3 and a needle penetration of 5 to
50 0.1 mm.
2. A process according to claim 1, wherein the substantially
amorphous polyalphaolefin starting material exhibits a tensile
strength between 0.5 and 10 N/mm.sup.2 and an elongation at break
greater than 200%.
3. A process according to claim 1, wherein the substantially
amorphous polyalphaolefin starting material is a binary or ternary
copolymer of the monomers 1-butene, propene and optionally
ethene.
4. A process according to claim 1, wherein the reduction in melt
viscosity with a radical donor is performed at temperatures between
150.degree. and 250.degree. C. under nitrogen atmosphere.
5. A process according to claim 1, wherein the radical donor is a
compound having a peroxo or diazo group and is used in an amount
between 0.05-3.0 wt. %, based on the weight of polyalphaolefin
starting material.
6. A process according to claim 5, wherein the radical donor is
dicumyl peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)-hexane or
2,2'-azo-bis(2-acetoxy-propane).
7. A process according to claim 1, wherein the substantially
amorphous polyalphaolefin produced has a quotient of melt viscosity
(at 90.degree. C.) and % elongation at break that is below 20.
8. A process according to claim 1, wherein the polyalphaolefin
starting material is an ethene/propene/1-butene terpolymer or a
propene/1-butene copolymer.
9. A process for reducing the melt viscosity and molecular weight
distribution of a substantially amorphous polyalphaolefin which
comprises:
decompositing a substantially amorphous polyalphaolefin of 0-20%
ethene, 25 to 95% propene and 3 to 75% 1-butene having a melt
viscosity at 190.degree. C. between 5,000-200,000 mPas, with a
0.05-3.0 wt. % of a radical donor compound having a peroxo or diazo
group, under shear stress at a temperature in the range of
150.degree.-250.degree. C.
10. A process according to claim 9, wherein the amorphous
polyalphaolefin is put under shear stress within an extruder or
kneader.
11. A process according to claim 9, wherein the substantially
amorphous polyalphaolefin product has a melt viscosity at
190.degree. C. between 1000 and 100,000 mPas, a density less than
0.90 g/m.sup.3, a needle penetration of 5 to 50 0.1 mm, a molecular
inhomogeneity below 6 and quotient of melt viscosity (at
190.degree. C.) and % elongation at break that is below 20.
Description
BACKGROUND OF THE INVENTION
The invention relates to a process for the production of largely
amorphous polyalphaolefins and the polymer obtained therefrom,
which are characterized by a softening point (measured by the ring
and ball method corresponding to DIN 52 011) between 70.degree. and
140.degree. C., a melt viscosity (at 190.degree. C.) between 1,000
and 100,000 mPas (determined by the methods described in ASTM D
3236), a density less than 0.90 g/cm.sup.3, a needle penetration
(determined by the methods described in DIN 52 010) of 5 to 50 0.1
mm and a molecular inhomogeneity, U=Mw/Mn-1 (determined by gel
permeation chromatography), of at most 6.
Reaction systems, consisting of reacting a polyolefin and a radical
donor are known. Homopolymers and copolymers of ethene can be
crosslinked in the presence of radical donors with energy input.
According to the rise in the molecular weight, elastomeric, i.e.,
rubber-like, products with improved dimensional stability at higher
temperatures or improved chemical resistance are obtained.
In addition, homopolymers based on propene can be
mechanically/thermally or radically decreased in molecular weight.
The end products, in comparison with the starting polymers, have a
higher melt flow index and, according to experience, a narrower
molecular weight distribution. The latter process step has gained
particular importance for the production of fiber material.
In the case of amorphous or largely amorphous polyalphaolefins,
comparable process steps have not been taken in practice, since a
practical use could not be seen. At most, an exception in some
respect is made in the case of atactic polypropylene (APP)
occurring during the production of isotactic polypropylene where
high molecular weight APP must be subjected to a decomposition step
to be able to be marketed at all. The starting product in such
cases has a softening point (ring and ball method) of over
150.degree. C. as well as a melt viscosity (at 190.degree. C.) of
over 200,000 mPas, often even far over 500,000 mPas. The
decomposition step usually leads to products with melt viscosities
(at 190.degree. C.) between 50,000 and 200,000 mPas, which have few
noncritical uses such as, for example, bitumen modification.
Because of this experience with polyolefins, it would be expected
that decomposition and crosslinking occur as competing reactions in
polyolefins, which are not synthesized exclusively from propene,
such as, for example, ethene/propene/1-butene terpolymers.
Therefore, no appreciable lowering of the molecular weight or
narrowing of the molecular weight distribution are expected to
occur.
SUMMARY OF THE INVENTION
It has been found that binary and ternary, largely amorphous
copolyalphaolefins with the following monomer composition are well
suited as starting materials for the process according to the
invention:
3 to 75% by weight of an alpha-olefin with 4 to 10 carbon
atoms;
25 to 95% by weight of propene;
0 to 20% by weight of ethene.
Preferred copolyolefin starting materials and the products produced
therefrom according to the invention, are either completely
amorphous or exhibit only slight crystallinity. Generally a degree
of crystallinity of 25%, determined by x-ray diffraction, is not to
be exceeded.
An object of the present invention is to provide a method for
reducing the melt viscosity and the molecular weight distribution
of a substantially amorphous polyalphaolefin.
It is another object of the present invention to provide amorphous
polyalphaolefins with a reduced melt viscosity and molecular weight
distribution while substantially maintaining other physical
properties.
It is a further object of the present invention to provide
amorphous polyalphaolefins with low melt viscosity, high cohesion
and high adhesion to substrates
Further objects will be apparent from the detailed disclosure and
claims which follow.
Surprisingly, it has been found that treatment of these
polyalphaolefins with radical donors not only lowers the molecular
weight but at the same time narrows the molecular weight
distribution. This means that molecular inhomogeneity U, defined by
the relation U=(Mw/Mn)-1, becomes smaller, where the molecular
weight data, Mw and Mn, represent the weight average and numerical
average molecular weight, respectively, as determined by gel
permeation chromatography.
It is also possible, despite the decomposition step, to
substantially maintain certain mechanical properties of the high
molecular weight starting material in the lower molecular weight
end product, such as, e.g., elongation at break.
Products of a specific melt viscosity obtained by the process
according to the invention have properties different in general
from products whose melt viscosity has the same value but which
were produced exclusively by direct polymerization. The products
according to the invention have, for example, an improved
sprayability, in comparison with products of similar viscosity
produced by direct polymerization. This is the object of German
patent application P 40 00 696.4, filed on Jan. 12, 1990.
In addition, the products produced according to the invention are
advantageously used as heavy coating compounds for carpets, as they
are described inter alia in EP-A-0 309 674. The low melt viscosity,
coupled with a high elongation at break, makes possible an increase
in the filler portion in the filled coating compound, as a result
of which the formulation can be reduced in price. Despite the
higher filler portion, such compounds have a sufficient mechanical
strength and flexibility. Since in contrast with usual compounds it
is possible to start from a lower melt viscosity in the polymer,
its processability such as its ability to be applied by knife and
brush is not adversely affected by the increase of the filler
portion.
Also with hot melt adhesives it is advantageous that the quotient
formed from melt viscosity and elongation at break be small. In
practice this means that the polymer, despite low melt viscosity,
which is favorable for certain working processes, such as, e.g.,
spraying, has sufficient cohesion and extensibility.
The starting products for the process according to the invention
are specifically polymerized on classic Ziegler catalysts or a
modified version thereof. Such a process is described, for example,
in DE-PS 23 06 667. Generally a largely amorphous polyalphaolefin
with a softening point (ring and ball method) between 70.degree.
and 140.degree. C., a melt viscosity at 190.degree. C. between
5,000 and 200,000 mPas, a density less than 0.90 g/cm.sup.3 and a
needle penetration of 100/25/5 (weight of needle: 100 g;
temperature 25.degree. C.; duration 5 s) between 5 to 50 0.1 mm at
a temperature above the softening point is reacted in the presence
of a radical donor under shear stress. As a result, the melt
viscosity (measured at 190.degree. C.) is reduced by at least
half.
The starting polyolefin typically has a tensile strength between
0.5 and 10 N/mm.sup.2 and a elongation at break of over 200%.
Within in the framework of this invention, polyalphaolefins which
are synthesized from the monomers propene, 1-butene and optionally
ethene are preferred. Particular suitable amorphous
polyalphaolefins are propene/1-butene/ethene terpolymers and
propene/1-butene copolymers obtainable under the trademark
VESTOPLAST.RTM., e.g., corresponding to DE-PS 23 06 667 or DE-PS 29
30 108. Other polymers which contain an alpha-olefin with 5 to 10
carbon atoms, such as, e.g., 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-heptene, 1-octene or 1-decene, besides or
instead of 1-butene, are suitable for use.
The radical donors used according to the invention are first of all
compounds containing peroxo groups or diazo groups. Such compounds
are offered, e.g., under the trademarks Luazo.RTM., Luperox.RTM.,
Luperco.RTM. and Interox.RTM. by the Pennwalt and Peroxid-Chemie
GmbH companies partly in substantially pure form, partly in dilute
form on a support. Such compounds have a 10-hour half-life in
benzene at temperatures between 50.degree. and 200.degree. C. They
are generally worked in at temperatures between 60.degree. and
200.degree. C. and are used in their function as radical donors at
temperatures between 100.degree. and 300.degree. C. The added
amounts are between 0.05 and 3% by weight, but preferably between
0.2 and 1% by weight. Typical representatives are dicumyl peroxide,
2,5-dimethyl-2,5-di-(t-butylperoxy)-hexane as well as
2,2'-azo-bis(2-acetoxy-propane), which have a 10-hour half life in
benzene at temperatures of about 115.degree. C., about 120.degree.
C. or about 190.degree. C., respectively.
The decomposition reaction is usually performed at temperatures
above the softening point of the polyalphaolefin, preferably
between 150.degree. and 250.degree. C. under a nitrogen atmosphere.
Suitable as apparatus are both extruders and stirring and mixing
units used in hot melt production. The level of shear applied to
the reaction mixture is not critical but it is preferably
equivalent to the shear stress generated within a Meili Laboratory
kneader such as is identified in the examples. Shear compounding to
an angular velocity of at least 10.sup.-1 is preferred.
Of course, parallel to or directly in connection with the
production process according to the invention, radically catalyzed
reactions such as, e.g., graft reactions with monomers containing
double bonds, which carry at least one functional group, can take
place. Suitable monomers are, for example, maleic anhydride,
fumaric acid, acrylic acid and methacrylic acid, itaconic acid,
aconitic acid and their derivatives such as, e.g., esters or amides
as well as vinyltrimethoxysilane (VTMO) and
3-methacryloxpropyltrimethoxysilane (MEMO; H.sub.2
C.dbd.C(CH.sub.3)COO(CH.sub.2).sub.3 Si(OCH.sub.3).sub.3. They are
usually used in amounts of 0.1 to 10% by weight, preferably 0.5 to
5% by weight, relative to the polyalphaolefin. In this way,
polymers with lowered melt viscosity, high cohesion and improved
adhesion with certain substrates such as metal, plastic or glass
surfaces are obtained.
Without further elaboration, it is believed that one skilled in the
art can, using the preceding description, utilize the present
invention to its fullest extent. The following preferred specific
embodiments are, therefore, to be construed as merely illustrative,
and not limitative of the remainder of the disclosure in any way
whatsoever.
In the foregoing and in the following examples, all temperatures
are set forth in degrees Celsius and unless otherwise indicated,
all parts and percentages are by weight.
The entire disclosures of all applications, patents and
publications, cited above and below, and of corresponding
application Federal Republic of Germany P 40 00 695.6, filed Jan.
12, 1990, are hereby incorporated by reference.
EXAMPLES
EXAMPLE 1
An ethene/propene/1-butene terpolymer (polyalphaolefin A), which
was previously mixed with 0.5% by weight of Luperco.RTM. 101 XLS
(2,5-dimethyl-2,5-di-(t-butylperoxy)-hexane, 45%), is kneaded under
a nitrogen atmosphere at a temperature of 185.degree. C. for 50
minutes in an oil-heated Meili laboratory kneader (alternately a
laboratory extruder can also be used). In this case air must be
excluded carefully (e.g. by previous flushing of the equipment with
nitrogen; optionally the addition of 0.2% by weight of antioxidant
such as, e.g., Irganox.RTM. 1010 is advantageous).
The properties of the starting product and end product are shown in
Table 1 below.
TABLE 1 ______________________________________ Starting Product End
Product (polyalpha- (polyalpha- Properties: olefin A) olefin 1)
______________________________________ Density, g/cm.sup.3 0.87
0.87 Composition: 5% by weight of ethene 65% by weight of propene
30% by weight of 1-butene Melt viscosity at 50,000 7,800
190.degree. C., mPas Softening point 110 103 (ring and ball)
.degree.C. Needle penetration 0.1 mm 14 17 Elongation at break, %
950 680 Molecular weight, Mw 91,000 60,000 Molecular weight Mn
11,000 10,000 Molecular inhomogeneity U 7.3 5 ##STR1## 52 11.4
______________________________________
An ethene/propene/1-butene terpolymer, produced by direct
polymerization on the same catalyst system as polyalphaolefin A,
having the same monomer composition and a melt viscosity (at
190.degree. C.) of 8,000 mPas, has an elongation at break of 300%.
The quotient of melt viscosity and elongation at break is 26.6.
EXAMPLE 2
The procedure as described in Example 1 is repeated with another
ethene/propene/1-butene terpolymer (polyalphaolefin B) as a
starting product. The starting product has a melt viscosity (at
190.degree. C.) of 8,000 mPas. Other properties of the starting
product and end product are shown in Table 2 below.
TABLE 2 ______________________________________ Starting Product End
Product (polyalpha- (polyalpha- Properties: olefin B) olefin 2)
______________________________________ Density, g/cm.sup.3 0.87
0.87 Composition: 5% by weight of ethene 65% by weight of propene
28% by weight of 1-butene Melt viscosity at 8,000 2,700 190.degree.
C., mPas Softening point 105 104 (ring and ball) .degree.C. Needle
penetration 0.1 mm 20 23 Elongation at break, % 300 170 Molecular
weight, Mw 61,000 45,000 Molecular weight Mn 7,500 7,300 Molecular
inhomogeneity U 7.1 5.1 ##STR2## 26.6 15.8
______________________________________
An ethene/propene/1-butene terpolymer produced by direct
polymerization on the same catalyst system as polyalphaolefin B
having the same monomer composition and a melt viscosity (at
190.degree. C.) of 2,900 mPas, has an elongation at break of 90%.
The quotient of melt viscosity and elongation at break is 32.2.
The preceding examples can be repeated with similar success by
substituting the generically or specifically described reactants
and/or operating conditions of this invention for those used in the
preceding examples.
From the foregoing description, one skilled in the art can easily
ascertain the essential characteristics of this invention, and
without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
* * * * *